EP0548976B1 - Olefinpolymerisation - Google Patents

Olefinpolymerisation Download PDF

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Publication number
EP0548976B1
EP0548976B1 EP92121955A EP92121955A EP0548976B1 EP 0548976 B1 EP0548976 B1 EP 0548976B1 EP 92121955 A EP92121955 A EP 92121955A EP 92121955 A EP92121955 A EP 92121955A EP 0548976 B1 EP0548976 B1 EP 0548976B1
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Prior art keywords
catalyst system
nickel
gram
alumina gel
substrate
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EP92121955A
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French (fr)
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EP0548976A1 (de
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Ronald Douglas Knudsen
Gil R. Hawley
Dennis Raymond Kidd
Randall Alan Porter
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Phillips Petroleum Co
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Phillips Petroleum Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond

Definitions

  • This invention relates to olefin polymerization.
  • this invention relates to a polymerization process and a novel polymerization catalyst system.
  • Olefin polymerization technology has long been developing with much of the efforts of those skilled in the art of olefin polymerization technology being towards the development and improvement of the solid component of polymerization catalysts.
  • the most common metal catalyst used in olefin polymerization is chromium, but others such as titanium have been suggested by the art. However, only a very few metals have been suggested by the art as being suitable for use as polymerization catalysts.
  • EP-A-0 548 753 which has to be considered under Article 54 (3) EPC, discloses a composition being suitable for polymerizing alpha-olefins, which composition comprises a pyridine compound, a clay compound and an organonickel compound.
  • Another object of this invention is to provide a process for the polymerization of olefin hydrocarbons.
  • a further object of this invention is to provide a novel method of preparing a catalyst system that can be utilized to promote the polymerization of olefins.
  • a catalyst system is provided as defined in claim 1, and its use in a process for polymerizing or copolymerizing olefins according to claim 12.
  • the inventive catalyst system is prepared by a method as defined in claim 9.
  • the catalyst system of this invention comprises, consists of, or consists essentially of a diluent, a substrate selected from alumina, silica, silicated alumina gel and mixtures thereof, a nickel compound wherein the nickel is in a zero oxidation state, and a pyridine component.
  • the diluent component of the catalyst system can be any inert diluent or medium which can suitably be used to maintain the substrate of the catalyst system in suspension during the polymerization process in which the catalyst system is utilized.
  • the diluent aids in the contacting of the monomer or monomers with the active polymerization catalyst.
  • the diluents can include aliphatic or aromatic hydrocarbons having from 3 to 12 carbon atoms.
  • a preferred diluent can be selected from the group consisting of benzene, xylene, toluene, cyclohexane, paraffinic hydrocarbons having from 4 to 12 carbon atoms and mixtures of two or more thereof.
  • substrate as used herein is not to be narrowly interpreted as being a mere inert component of the catalytic system. It is believed, without wanting to be bound to any particular theory, that while the substrate does not specifically react with the polymerizable olefins of the polymerization reaction, due to its physical properties and the manner in which it cooperates with the metal catalyst component of the catalytic system, the type and physical properties of the substrate can impart or enhance the polymerization activity of the catalytic system.
  • the substrate of the catalyst system is selected from the group consisting of alumina, silica, silicated alumina gel and mixtures of two or more thereof.
  • the most preferred substrate for use in the catalyst system of this invention is a silicated alumina gel as prepared by the methods described at length herein.
  • the specific nickel compound utilized as a component of the catalyst system is a critical feature or element of this invention in that it is believed that there are no known nickel polymerization catalyst systems that use a nickel catalyst that does not have a phosphine or arsenic ligand on the metal atom. It is believed that it is the specific interaction of the nickel compound of the catalyst system in combination with the pyridine component with the substrate which provides for the polymerization catalytic activity that is observed with this invention.
  • the preferred nickel compound component of this invention is one that does not comprise a phosphine or an arsenic ligand but has a nickel atom in the zero oxidation state.
  • the most preferred nickel compound for use in this invention is known by its chemical name bis(1,5-cyclooctadiene) nickel(0).
  • the chemical compounds that can suitably be used as the pyridine component of the catalyst system are pyridine based compounds having the following structural formula: wherein C is a carbon atom, N is a nitrogen atom, and R can be one of either hydrogen, an alkyl group or a carboxylic acid group.
  • the preferred compounds for use as the pyridine component of the catalyst system are pyridine carboxylic acid compounds.
  • the most preferred pyridine component of the catalyst system is picolinic acid.
  • picolinic acid refers to the chemical compound pyridine-2-carboxylic acid, which has the chemical formula of C 6 H 5 O 2 N and the chemical structure as follows:
  • the most preferred substrate material for use in the invention is a silicated alumina gel that is prepared by mixing an acidified slurry of boehmite or aluminum oxide hydroxide, AlO(OH), with a silicate solution followed by the addition of a base suitable for inducing the formation of a silicated alumina gel comprising, consisting of, or consisting essentially of silica.
  • a silicated alumina gel is recovered and is utilized as the substrate of the invention.
  • the acidified slurry of boehmite and aluminum oxide hydroxide, respectively, can be prepared by mixing with a suitable solvent, by any suitable means known in the art, a boehmite material that is reduced in size to form a suitably sized fine powder for forming a slurry. It is generally desirable that the solvent used in preparing the acidified slurry of boehmite be water and that the amount of starting boehmite material be present in the slurry in an amount in the range of from 10 grams boehmite to 200 grams boehmite per 1000 grams water.
  • the weight ratio of boehmite to water in the boehmite slurry is not limited to 200 grams boehmite per 1000 grams water.
  • a preferred range for the amount of boehmite in the aqueous slurry is from 25 grams boehmite to 150 grams boehmite per 1000 grams water; but, the most preferred weight ratio of boehmite to water in the boehmite slurry is in the range of from 50 grams boehmite to 100 grams boehmite per 1000 grams water.
  • the boehmite material is dispersed in the solvent by adding an acid or acidifying agent to acidify the slurry and to form the acidified slurry of boehmite.
  • an acid or acidifying agent Any acid can be utilized to form the acidified slurry of boehmite that suitably gives a slurry with the desired properties. It is preferred, however, that the acid be selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, acetic acid and mixtures of two or more thereof.
  • the most preferred acid for use as an acidifying agent is nitric acid (HNO 3 ).
  • the amount of acid employed in acidifying the mixture of boehmite and solvent can be any amount suitable for and effective in dispersing the boehmite in the solution and can range from 1 gram concentrated acid to 50 grams concentrated acid per 1000 grams of solvent.
  • a silicate solution is added to the slurry and mixed sufficiently to provide a homogeneous mixture.
  • the silicate solution used in forming the homogeneous mixture is preferably a solution of sodium silicate and water.
  • the sodium silicate solution is prepared by acidifying a dilute aqueous mixture of sodium silicate with any suitable acid that will cause a solution, but not a gel, to be formed.
  • the aqueous mixture of sodium silicate will generally comprise from 1 gram sodium silicate to 80 grams sodium silicate per 100 grams water.
  • the aqueous mixture of sodium silicate will have from 10 grams sodium silicate to 70 grams sodium silicate per 100 grams water; but, most preferably, the weight ratio of sodium silicate per water in the aqueous mixture of sodium silicate is from 20 to 60.
  • the agent used to acidify the aqueous mixture of sodium silicate to form the silicate solution be an acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, acetic acid and mixtures of two or more thereof.
  • the most preferred acidifying agent or acid is nitric acid (HNO 3 ).
  • the amount of acid employed in acidifying the aqueous mixture of sodium silicate can be any suitable amount necessary to form the solution; but, preferably, it is an amount such as to give a solution having a pH in the range of from 1 to 3. Most preferably, the amount of acid utilized will be that amount necessary to provide a silicate solution pH of from 1.5 to 2.0.
  • any suitable method known in the art can be used to suitably mix the acidified slurry of boehmite and the silicate solution to form a homogenized mixture or mixture.
  • the mixing or blending time can range upwardly to 60 minutes, but it is generally less than 60 minutes. Preferably, the mixing time will be in the range of from 2 minutes to 30 minutes.
  • a base compound is added to the mixture which is suitable for inducing the formation of a gel material comprising, consisting of, or consisting essentially of silicated alumina.
  • base compounds suitable for inducing the formation of the gel include, but are not limited to, alkali metal hydroxides, ammonium hydroxide, ammonia, and urea. Ammonium hydroxide is the preferred base compound.
  • the gel formed by aforedescribed process can be utilized as the most preferred substrate of the invention described herein.
  • the gel or silicated alumina gel is recovered by any suitable means known in the art such as, for example, filtration, and thereafter washed to remove sodium ions and other surface impurities or contaminants.
  • the washed silicated alumina gel is then dried to remove water by any suitable means known in the art.
  • Spray drying methods are among the suitable drying methods that can be used to dry the washed gel. Examples of such suitable spray drying methods and apparatuses are listed and described in Perry's Chemical Engineers' Handbook, Sixth Edition , Edited by D. W. Green (McGraw-Hill, 1984) at pp. 20-54 through 20-58.
  • the activity of the catalyst system toward promoting olefin polymerization is improved as the presence of silica contained in the silicated alumina gel is increased upwardly to about 75 weight percent of the total weight of the silicated alumina gel and perhaps greater than 75 weight percent depending upon the type and physical properties of alumina used in the preparation of the silicated alumina.
  • the preferred amount of silica contained in the silicated alumina gel substrate is in the range of from 10 weight percent to 75 weight percent of the silicated alumina gel. Most preferably, the amount of silica contained in the silicated alumina gel substrate can range from 15 weight percent to 66 weight percent.
  • the silicated alumina gel prepared by the method described herein typically will have pore sizes in the range of 30-80 nm (300-800 ⁇ ), pore volumes in the range of 0.4 to 1.25 cc/gram and surface areas in the range of 200 to 350 m 2 /gram.
  • the value representing "pore volume”, as referred to herein, is determined by the method of mercury intrusion porosimetry as completely described by the ASTM method D4284-88 entitled "Standard Test Hethod for Determining Pore Volume Distribution of Catalysts By Mercury Intrusion Porosimetry". This standard ASTM test method D4284-88 is incorporated herein and made a part hereto by reference.
  • the catalyst system of this invention can be used to polymerize at least one mono-1-olefin containing 2 to 8 carbon atoms per molecule, preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene.
  • the invention is most preferred in producing ethylene homopolymers.
  • the invention may also be used in the production of copolymers from mixtures of ethylene and of one or more comonomers selected from 1-olefins containing 3 to 8 carbon atoms per molecule.
  • Exemplary comonomers include aliphatic 1-olefins, such as propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene and other higher olefins and non-conjugated diolefins such as 1,4-pentadiene, 1,5-hexadiene, and other such diolefins and mixtures thereof.
  • the polymers are preferably prepared by a slurry polymerization process whereby the polymerizable olefins are contacted with a slurry of the inert diluent or medium and the substrate with the slurry having contained therein the nickel compound catalyst and a concentration of a pyridine component.
  • An in-situ preparation of the catalyst system is made by adding to the slurry of diluent and substrate the nickel compound wherein the nickel is in a zero oxidation state and a pyridine component.
  • the substrate will be present in the diluent in the form of finely divided, suspended solids in the range of from 0.01 grams to 100 grams substrate per 100 grams diluent.
  • the nickel compound in combination with the pyridine component is dispersed in the diluent in an amount such that the nickel metal will be present in the range of from 0.1 grams to 10 grams nickel metal per 100 grams substrate.
  • the amount of nickel compound dispersed in the diluent can be such that the amount of nickel metal in the diluent will range from 0.2 grams nickel metal to 5.0 grams nickel metal per 100 grams substrate. Most preferably, the amount of nickel compound dispersed in the diluent will be such that the nickel metal will be present from 0.5 grams nickel metal to 2.5 grams nickel metal per 100 grams substrate.
  • the quantity of the pyridine component utilized in the catalyst system will depend upon the amount of nickel compound present in the diluent with the molar ratio of the pyridine component to the nickel compound being in the range of from 0.25:1 to 2.0:1.
  • the preferred molar ratio of the pyridine component to nickel compound is in the range of from 0.5:1 to 1.5:1 and, most preferably, the molar ratio can range from 0.75:1 to 1.25:1.
  • the process of this invention is generally carried out under conditions suitable for the polymerization of polymerizable olefins.
  • a temperature of 60°C to 110°C is employed.
  • the process pressure can vary from 110 psia to 700 psia (0.76-4.8 MPa) or higher.
  • the substrate is kept in suspension in the diluent and the catalyst system is contacted with the monomer or monomers at sufficient pressure to maintain the diluent or medium and at least a portion of the monomer or monomers in the liquid phase.
  • the medium and temperature are thus selected such that the polymer is produced as solid particles and is recovered in that form.
  • the feasible temperature range is 66°C to 110°C (150°F to 230°F).
  • This example illustrates the method of preparation of the silicated alumina substrate employed as a component of the catalyst system of this invention.
  • the boehmite starting materials came from two main commercial sources. Catapal A and Catapal D were obtained from Vista Chemical while Pural 200, Pural 400, and Pural 40/200 were obtained from Condea Chemie. The sodium silicate used in the silication of the boehmite starting materials were obtained from Brainard Chemical.
  • the basic method for the silication of a boehmite consisted of slurrying about 60.9 grams of the boehmite, A1O(OH), in about 1.0 liter of water, then adding 10 ml of concentrated nitric acid, HNO 3 , to disperse the A1O(OH). This was stirred for ten minutes prior to adding the silicate solution.
  • the silicate solution was prepared by diluting about 44.0 grams of sodium silicate with about 132 grams of water followed by rapidly adding 50 ml of concentrated HNO 3 while vigorously stirring the solution. The silicate solution was then added to the A1O(OH) slurry, stirred for ten minutes and then gelled by adding 100 ml of NH 4 OH.
  • the mixture was filtered and washed with four 1 liter portions of H 2 O.
  • the first washing also contained 30 grams of NH 4 NO 3 to aid in Na cation removal.
  • the samples were dried for 3 hrs. at 100°C or spray dried with a 95°C outlet temperature. Samples for pore size analysis were calcined at 500°C for 3 hrs.
  • Nitrogen pore size distributions were determined on a Quantachrome-6 instrument. Surface areas were determined by multi-point BET methods using the Quantachrome-6. Mercury pore size distributions were determined by the intrusion method.
  • This example demonstrates the use of the catalyst system in the polymerization of polymerizable olefins, and it further illustrates the improvement in catalytic activity achievable by use of a silicated alumina substrate in the catalyst system of this invention.
  • Ethylene was polymerized in a standard stirred stainless steel reactor.
  • the reactor was charged with about 350 ml toluene and the specific alumina or silicated alumina substrate listed in Table I below with the preparation of each substrate being generally described in Example I.
  • a quantity ranging from 0.05 grams to 0.15 grams of bis (1,5-cyclooctadiene) nickel(0) and a quantity of picolinic acid ranging from 0.032 grams to 0.084 grams were added to the slurry of substrate and diluent.
  • melt index (MI) of the polymer produced by the method of this example was determined in accordance with ASTM D1238, condition 190/2.16 and its high load melt index (HLHI) was determined in accordance with ASTM D1238, condition 190/21.60.
  • results from this experiment demonstrate that the catalyst system described herein is effective for promoting the polymerization of polymerizable olefins.
  • results further demonstrate the unexpected result that a silicated substrate prepared by the methods described herein can be used to enhance the catalytic activity of the aforementioned polymerization catalyst system.

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Claims (12)

  1. Katalysatorsystem, enthaltend ein verdünnungsmittel, ein unter Aluminiumoxid, Siliciumdioxid, siliciertem Aluminiumoxidgel und Gemischen davon ausgewähltes Substrat, eine Nickelverbindung, bei der das Nickel in einem nullwertigen Oxidationszustand vorliegt, und eine Pyridinkomponente.
  2. Katalysatorsystem nach Anspruch 1, wobei das Verdünnungsmittel unter Benzol, Xylol, Toluol, Cyclohexan, Paraffinkohlenwasserstoffen mit 4 bis 12 Kohlenstoffatomen und Gemischen davon ausgewählt wird.
  3. Katalysatorsystem nach Anspruch 1 oder 2, wobei es sich bei der Nickelverbindung um Bis-(1,5-cyclooctadien)-nickel(0) handelt.
  4. Katalysatorsystem nach einem der vorstehenden Ansprüche, wobei es sich bei der Pyridinkomponente um Picolinsäure handelt.
  5. Katalysatorsystem nach einem der vorstehenden Ansprüche, wobei das Substrat im Verdünnungsmittel in einer Menge von 0,01 bis etwa 100 g Substrat pro 100 g Verdünnungsmittel vorhanden ist und die Nickelverbindung in Kombination mit der Pyridinkomponente im Verdünnungsmittel in einem solchen Anteil dispergiert ist, daß das Nickelmetall in einer Menge von 0,1 bis 10 g Nickel pro 100 g Substrat vorhanden ist und das Molverhältnis der Nickelverbindung zur Pyridinkomponente im Bereich von 0,5:1 bis 4:1 liegt.
  6. Katalysatorsystem nach einem der vorstehenden Ansprüche, wobei es sich beim Substrat um siliciertes Aluminiumoxidgel mit einem Gehalt an Siliciumdioxid von 10 bis 75 Gew.-%, bezogen auf das Gesamtgewicht des silicierten Aluminiumoxidgels, handelt.
  7. Katalysatorsystem nach einem der vorstehenden Ansprüche, wobei das Substrat gemäß folgenden Stufen hergestellt wird:
    (a) Vermischen einer angesäuerten Aufschlämmung von Aluminiumoxidhydroxid mit einer silicatlösung unter Bildung eines Gemisches; und
    (b) Zugeben einer Base, die sich zur Herbeiführung der Bildung eines Siliciumdioxid enthaltenden silicierten Aluminiumoxidgels, das als Substrat verwendet werden kann, eignet, zum Gemisch.
  8. Katalysatorsystem nach Anspruch 7, wobei die angesäuerte Aufschlämmung aus Aluminiumoxidhydroxid hergestellt wird, indem man 10 bis 200 g Aluminiumoxidhydroxid in etwa 1000 g Wasser aufschlägt und anschließend eine säureverbindung in einer Menge von 1 bis 50 g konzentrierte Säure pro 1000 g Wasser zugibt, und wobei die silicatlösung durch Verdünnen von 1 bis 80 g Natriumsilicat mit etwa 100 g Wasser unter anschließender Zugabe einer Säureverbindung in einer solchen Menge, daß sich eine silicatlösung mit einem pH-Wert von 1 bis 3 ergibt, hergestellt wird.
  9. Verfahren zur Herstellung des Katalysatorsystems nach einem der Ansprüche 1 bis 8, umfassend folgende Stufen:
    (a) Herstellen eines silicierten Aluminiumoxidgels mit einem Gehalt an Siliciumdioxid und
    (b) Einverleiben einer Nickelverbindung, wobei das Nickel in einem nullwertigen Oxidationszustand vorliegt, in einer Kombination mit einer pyridinkomponente in eine Aufschlämmung, die das silicierte Aluminiumoxidgel und ein Verdünnungsmittel enthält.
  10. Verfahren nach Anspruch 9, umfassend folgende Stufen:
    (a) Vermischen einer angesäuerten Aufschlämmung aus Aluminiumoxidhydroxid mit einer silicatlösung unter Bildung eines Gemisches;
    (b) Zugeben einer zur Herbeiführung der Bildung eines silicierten Aluminiumoxidgels mit einem Gehalt an Siliciumdioxid geeigneten Base;
    (c) Gewinnen des silicierten Aluminiumoxidgels;
    (d) Waschen des silicierten Aluminiumoxidgels unter Entfernung von Verunreinigungen;
    (e) Trocknen des auf diese Weise gewaschenen silicierten Aluminiumoxidgels;
    (f) Einverleiben einer Nickelverbindung, wobei das Nickel in einem nullwertigen Oxidationszustand vorliegt, in Kombination mit einer Pyridinkomponente in eine Aufschlammung, die das silicierte Aluminiumoxidgel und ein Verdünnungsmittel enthält.
  11. Verfahren nach Anspruch 9 oder 10, wobei die Menge der der Aufschlämmung einverleibten Nickelverbindung so beschaffen ist, daß sich ein Anteil an Nickelmetall in der Aufschlammung von 0,1 bis 10 g Nickelmetall pro 100 g des silicierten Aluminiumoxidgels ergibt und das Molverhältnis der Nickelverbindung zur Pyridinkomponente in der Aufschlämmung 0,5:1 bis 4:1 beträgt.
  12. Verwendung eines Katalysatorsystems nach einem der Ansprüche 1 bis 8 in einem Verfahren zur Polymerisation oder Copolymerisation von Olefinen.
EP92121955A 1991-12-24 1992-12-23 Olefinpolymerisation Expired - Lifetime EP0548976B1 (de)

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US07/813,169 US5338812A (en) 1991-12-24 1991-12-24 Olefin polymerization
US813169 1991-12-24

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US6281309B1 (en) 1997-01-08 2001-08-28 Eastman Chemical Company Flourinated solid acids as catalysts for the preparation of hydrocarbon resins
US6403526B1 (en) 1999-12-21 2002-06-11 W. R. Grace & Co.-Conn. Alumina trihydrate derived high pore volume, high surface area aluminum oxide composites and methods of their preparation and use
RU2259232C2 (ru) * 1999-12-21 2005-08-27 В.Р.Грейс Энд Ко.-Конн. Полученные из тригидрата оксида алюминия композиты оксида алюминия с большим объемом пор и большой площадью поверхности, способы их получения и применения
DE10257240B4 (de) * 2002-12-04 2005-03-10 Coty Bv Kosmetische Zusammensetzung mit elektrischen Ladungsträgern und deren Verwendung
JP4382030B2 (ja) 2005-11-15 2009-12-09 富士通マイクロエレクトロニクス株式会社 半導体装置及びその製造方法

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SG44535A1 (en) 1997-12-19
ES2093172T3 (es) 1996-12-16
CA2085952C (en) 1998-05-19
NO301017B1 (no) 1997-09-01
DE69212789D1 (de) 1996-09-19
CA2085952A1 (en) 1993-06-25
FI925856A (fi) 1993-06-25
FI925856A0 (fi) 1992-12-23
US5426080A (en) 1995-06-20
GR3021088T3 (en) 1996-12-31
DK0548976T3 (da) 1996-09-02
US5338812A (en) 1994-08-16
EP0548976A1 (de) 1993-06-30
FI108447B (fi) 2002-01-31
AU643395B2 (en) 1993-11-11
BR9204184A (pt) 1993-06-29
AU2533992A (en) 1993-07-01
MX9205871A (es) 1993-06-01
TW243456B (de) 1995-03-21
CN1073685A (zh) 1993-06-30
ZA927332B (en) 1993-04-21
CN1073686A (zh) 1993-06-30
DE69212789T2 (de) 1996-12-19
ATE141293T1 (de) 1996-08-15
HUT65780A (en) 1994-07-28
NO925002D0 (no) 1992-12-23
KR0172455B1 (ko) 1999-03-30
CN1047599C (zh) 1999-12-22
HU212038B (en) 1996-01-29
CN1030456C (zh) 1995-12-06
JPH05247129A (ja) 1993-09-24
JP2713842B2 (ja) 1998-02-16
HU9204128D0 (en) 1993-04-28

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